International Journal of Advanced Research in Chemical Science
Volume-3 Issue-12, 2016, Page No: 9-24
Amphiphilic Block Copolymers of Ethylene Oxide and 2 Methacryloyloxyethyl Ferrocenecarboxylate: Self-Assembly Behavior, Thermal and Electrochemical Properties
Margarita Droulia, Vasiliki Asimopoulou-Marinou, Marinos Pitsikalis,Patrina Paraskevopoulou
1.Industrial Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens Greece
Citation : Margarita Droulia, Vasiliki Asimopoulou-Marinou, Marinos Pitsikalis,Patrina Paraskevopoulou,Amphiphilic Block Copolymers of Ethylene Oxide and 2 Methacryloyloxyethyl Ferrocenecarboxylate: Self-Assembly Behavior, Thermal and Electrochemical Properties International Journal of Advanced Research in Chemical Science. 2016;3(12):9-24.
Abstract
Well defined redox responsive amphiphilic block copolymers of ethylene oxide, EO, and 2- methacryloyloxyethyl ferrocenecarboxylate, MAEFc were prepared by atom transfer radical polymerization (ATRP). The synthetic procedure was monitored by size exclusion chromatography (SEC) and the block
copolymers were characterized using
1H NMR spectroscopy. The self-assembly behavior of these amphiphilic copolymers was studied in aqueous solutions and in acetonitrile, both selective solvents for the PEO block. The formation of supramolecular structures (micelles and micellar aggregates) was revealed by Dynamic Light Scattering (DLS) using the CONTIN algorithm. The thermal properties of the block copolymers were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Cyclic voltammetry of PEO-b-PMAEFc copolymers in CHCl
3 solutions revealed a single redox process, a quasireversible oxidation wave with very slow kinetics, attributed to the Fe
II Fe
III oxidation of the ferrocenyl units. The oxidation of the copolymers became more difficult and that the kinetic reversibility of the redox process was
diminished as the PEO/PMAEFc ratio in the polymer chain increased.